US4066470A - Method for the treatment of finely grained material, particularly for the precalcining of cement - Google Patents
Method for the treatment of finely grained material, particularly for the precalcining of cement Download PDFInfo
- Publication number
- US4066470A US4066470A US05/665,327 US66532776A US4066470A US 4066470 A US4066470 A US 4066470A US 66532776 A US66532776 A US 66532776A US 4066470 A US4066470 A US 4066470A
- Authority
- US
- United States
- Prior art keywords
- zone
- fuel
- precalcining
- preoxidation
- conduit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/434—Preheating with addition of fuel, e.g. calcining
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
- F27B7/2016—Arrangements of preheating devices for the charge
- F27B7/2025—Arrangements of preheating devices for the charge consisting of a single string of cyclones
- F27B7/2033—Arrangements of preheating devices for the charge consisting of a single string of cyclones with means for precalcining the raw material
Definitions
- the invention relates to a method and mechanism for the thermal treatment of pulverulent or finely grained material, and particularly for the calcining of cement in several steps whereby the raw material is first preheated in a precalcining step and finally the calcining is completed in a furnace. More particularly, the invention relates to improvements in the precalcining step in cooperation with the calcining step so that controlled heating and controlled oxidation takes place in precalcining as the material is admixed with partially oxidized fuel and oxygen.
- a conventional process involves calcining and sintering which take place consecutively in a rotary kiln in two separate portions so that the rotary kiln solely performs a sintering function, and another part connected in series operates on added calcining material particles in an airstream.
- the precalcining device is a cyclone heat exchanger, and permits the rotary kiln to be made smaller in size.
- a more expensive structure is involved than with a heat exchanger that does not rotate but is subjected only to static load.
- it is possible to reduce the size of the rotary kiln this brings about a savings in cost of construction and also a savings in space required, and this can be accomplished by a more effective improved precalcination structure and operation.
- a heat supply is provided in a separate special combustion zone.
- this combustion zone it is important that a predetermined maximum temperature must not be exceeded because excessive temperatures will result in the danger of caking of the material interfering with the normal operation of the device.
- Attempts have been made to provide separate special combustion chambers which have been relatively expensive from a structural standpoint, and these are positioned between the preheater and the rotary kiln functioning for sintering wherein a special complex intermixture of raw material and fuel is attempted to prevent peaks in temperature, and such chambers insuring this function have been found to be expensive in construction and not wholly satisfactory.
- the aforementioned difficulties have been overcome in a simplified and reliable way.
- a reliable ignition of the combustible fuel as well as a uniform combustion at relatively low temperatures has been insured.
- the fuel is ignited and partially oxidized in precombustion step and combined with the hot oxygen containing gas stream from the furnace, and this mixture is admixed with a substantial part of the raw material to be treated which is further oxidized in a precalcination zone.
- partial oxidation first takes places with the fuel supply, and the fuel is ignited reliably and uniformly. In the first combined completely ignited and partially oxidized condition, it is admixed with the majority of the raw material to be treated.
- the partially oxidized fuel is there further burned in intimate mixture with the material to carry out the precalcination.
- a completely uniform distribution of the combustible material and the raw material take place, and delays in ignition or combustion as have occurred with methods heretofore available wherein too great a density of material present, are reliably prevented. Local overheatings are also prevented.
- a further object of the invention is to provide an improved method and structure for precalcination of cement wherein a more uniform and a more effective precalcination takes place to improve the capacity of precalcination apparatus.
- a still further object of the invention is to provide an improved precalcination arrangement wherein a more uniform mixing occurs between heated gases and oxygen and raw material, and wherein a particularly more uniform heating of the material occurs without the possibility of localized areas of high temperature occurring.
- a still further object of the invention is to provide an improved arrangement wherein a partial oxidation of the fuel takes place and oxygen and partially oxidized fuel is supplied to an admixing area for uniform distribution of the fuel and oxygen through the material and the completion of combustion of the fuel and oxidation of the material to be precalcined.
- partial oxidation of the fuel takes place in the hot oxygen containing gas stream that is received from the calcination furnace, and thereafter the mixture of partially oxidized fuel and the gas is combined with the raw material.
- parts of the normal oxygen containing streams of gas are used for the partial oxidation of the fuel.
- the mixture of partially oxidized fuel and gas is combined thoroughly with the raw material, and upon the residual burning up of the fuel, the precalcination is completed with the optimization of use of total fuel energy.
- additional oxygen is supplied to the stream of gas after partial oxidation at a controlled rate.
- This addition of oxygen to the oxygen in the gas coming from the rotary kiln can be adjusted as desired to adapt to varying operation of the rotary kiln and varying rates of material treatment.
- a flame guidance structure is provided which has a separate preoxidation zone, and an admixing area for the calcination zone wherein the calcination zone is optimally positioned relative to the position of the ignition chamber, combustion chamber and burner as well as the location and direction of additional fuel supply and oxygen supply nozzles.
- the main sintering furnace or kiln are provided with a standpipe or vertical conduit provided for receiving at its lower end the furnace exhaust gases.
- Fuel is added in a preoxidation zone in the conduit wherein the fuel is partially oxidized with the oxygen from the exhaust gases.
- Material feed is supplied above the fuel feed with the distance between the fuel feed and material feed being critical so that no raw material reaches the area of fuel introduction and the fuel flow path is limited so that only partial oxidation takes place before admixing occurs.
- a completely uniform flame can develop so that an accurately adjustable temperature profile can be obtained which is not disturbed throughout the combustible material.
- a deflecting device is located between the precombustion zone and the admixing area where the raw material is added. This deflecting device prevents larger particles of material from dropping downwardly and entering the fuel ignition and preoxidation area. The deflected materials are carried upwardly by the stream of gas and do not reach the oxidation chamber. This prevents particles of material from disturbing the preoxidation and flame distribution.
- a combustion chamber for a partial oxidation of fuel with the combustion opening into the gas conduit leading from the rotary kiln.
- a partial preoxidation occurs in the separate chamber, and adjustment of fuel and oxygen supply can be made in accordance with the requirements of flame expansion and speed of ignition.
- Such a chamber makes it possible for completely uniform preoxidation, and the development of a temperature profile favorable to the thermal process required in the precalcination zone.
- This separate combustion chamber may be arranged concentrically about the gas conduit and enables a uniform distribution peripherally into the gas conduit.
- a preferred distance between the fuel feed through the preoxidation zone to the point of material supply to the admixing area is one-fourth of the theoretical flame length.
- the distances between one-fourth of the theoretical flame length and not greater than the flame length are preferably much closer to one-fourth of the flame length so that the combustion of the flame is not so cooled by the stream of cooler raw material flowing into the oxidizing flame so that unequal or overheating will not occur.
- FIG. 1 is an elevational view shown partially in section, and shown somewhat schematically of a mechanism operating in accordance with the principles of the present invention
- FIG. 2 is a somewhat schematic elevational view with portions in section showing another form of the invention.
- FIG. 3 is a somewhat schematic horizontal sectional view taken substantially along III--III of FIG. 2.
- FIGS. 1 and 2 which show separate embodiments, similar parts are indicated with like numerals.
- a main rotary kiln or furnace 1 is shown with portions omitted.
- the rotary kiln will have means to drive it in rotation with a burner, not shown, and means for removing the fully calcined cement.
- Discharge gases from the rotary kiln 1 pass outwardly through the inlet chamber 2 and flow upwardly through a vertical standpipe or conduit 16.
- the inlet chamber 2 also receives the precalcined cement which flows down through a material feed conduit 3 from a heat exchange cyclone 4.
- the cyclone receives the precalcined cement which is treated in a manner which will be described.
- the gas outlet from the cyclone is shown at 5, and further cyclone preheater steps and devices may be provided as will be recognized by those versed in the art.
- the cyclone is supplied with preheated, precalcined cement through a main gas conduit 6.
- Raw material is supplied through an inlet material feed conduit 7.
- Heated gas containing oxygen flows vertically upwardly through the vertical conduit 16, and fuel is supplied through burners 9 into a preoxidation zone 18.
- the ignited fuel is partially burned or partially oxidized and flows upwardly with additional oxygen into a precalcining zone 17.
- a precalcining zone 17 At the lower end of the precalcining zone 17 is an admixing area 19 which receives the flow of raw material through the inlet conduit 7.
- the flow of fuel to the burners 9 is controlled by fuel control valve 9a.
- additional oxygen is also supplied in a controlled amount through oxygen supply lines 11 leading to the preoxidation zone 18.
- the flow of oxygen is controlled by valve means 11a, and regulation of the fuel and oxygen flow as a function of flow of gases upwardly through the conduit 16 and as a function of flow of material through the inlet line 7 can be controlled.
- valve means 11a may be manually adjusted in accordance with operational values and with the furnace capacity or automatic equipment may be provided which measure flows rates and temperatures.
- a deflector device 8 is provided. This is shown preferably in the form of a laterally slidable plate which is movable laterally by hand or by an operating device shown by the arrowed line 14. Other deflecting devices may be provided which will perform the objectives, and these may be in the form of deflecting partially open grids or screens.
- the deflecting device functions to reliably permit the partially oxidized burning gases to flow upwardly, but to prevent heavy particles from falling directly downwardly into the preoxidation area 18.
- the material flow inlet 7 shown as set at an angle to the vertical upward flow of gases, the lighter particles will tend to be deflected and distributed laterally across the conduit 16 when they enter the admixing zone 19, and the heavier particles will drop downwardly to be deflected laterally outwardly by the deflecting plate 8.
- the fuel inlets and the oxygen inlets may be diametrically opposed as illustrated, or a plurality may be provided arranged circumferentially around the preoxidation zone 18.
- additional material feed inlet may be provided with deflecting plates arranged to deflect heavier particles inwardly and insure their distribution across the admixing zone.
- exhaust gas from the rotary kiln which contains oxygen to an appreciable degree flows outwardly through the inlet chamber 2 and upwardly through the main gas conduit 6.
- Ignited gas flows in through the burner inlets 9 and additional oxygen is supplied in a controlled amount to influence the combustion temperatures of the flame developed and to control the degree of preoxidation which takes place.
- the preoxidized stream of gas after passing the deflecting plate drags with it the raw material to be calcined, which flows inwardly through the conduit 7.
- the length of the flame is so adjusted and so located that the upper part of the flame at which the material is supplied at the admixing zone 19 does not exceed 1100° C. This will not result in a caking of the material being precalcined.
- the burners are also located relative to the inlet opening 7a for the raw material so that the vertical distance between the burners 9 and the opening 7a is at least 1/4 of the theoretical flame length. By this vertical spacing the material introduction takes place in the most favorable hot part of the combustion zone. The distance should be somewhere near 1/4 of the theoretical flame length and less than the total flame length so that the combustion is cooled by the entering cooler material which prevents overheating of the material.
- a separate combustion chamber 10 is provided preferably situated annularly around the vertical conduit 16. In the combustion chamber, ignition of the fuel takes place, and a partial oxidation occurs. With this arrangement, it is insured that the fuel is uniformly ignited and partially burning before being discharged into the preoxidation zone 18. Circumferentially spaced openings such as 12 lead from the combustion area 10 into the conduit 16. Gas is supplied through the burner 9 from a line controlled by gas flow control valve 9a. Oxygen is also supplied through a line controlled by a valve 11a to obtain the initial ignition of the combustible fuel.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
- Crucibles And Fluidized-Bed Furnaces (AREA)
- Muffle Furnaces And Rotary Kilns (AREA)
- Furnace Details (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/678,951 US4062691A (en) | 1975-04-21 | 1976-04-21 | Method for the thermal treatment of finely granular material, particularly for the calcining of cement |
US05/833,231 US4187071A (en) | 1975-03-10 | 1977-09-14 | Method for the treatment of finely grained material, particularly for the precalcining of cement |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DT2510312 | 1975-03-10 | ||
DE2510312A DE2510312C3 (de) | 1975-03-10 | 1975-03-10 | Verfahren zur thermischen Behandlung von feinkörnigem Gut, insbesondere zum Brennen von Zement |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/678,951 Continuation-In-Part US4062691A (en) | 1975-04-21 | 1976-04-21 | Method for the thermal treatment of finely granular material, particularly for the calcining of cement |
US05/833,231 Division US4187071A (en) | 1975-03-10 | 1977-09-14 | Method for the treatment of finely grained material, particularly for the precalcining of cement |
Publications (1)
Publication Number | Publication Date |
---|---|
US4066470A true US4066470A (en) | 1978-01-03 |
Family
ID=5940902
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/665,327 Expired - Lifetime US4066470A (en) | 1975-03-10 | 1976-03-09 | Method for the treatment of finely grained material, particularly for the precalcining of cement |
Country Status (11)
Country | Link |
---|---|
US (1) | US4066470A (de) |
JP (1) | JPS51112833A (de) |
AU (1) | AU507678B2 (de) |
BR (1) | BR7601421A (de) |
CS (1) | CS219873B2 (de) |
DE (1) | DE2510312C3 (de) |
DK (1) | DK100276A (de) |
ES (1) | ES445778A1 (de) |
FR (1) | FR2303772A1 (de) |
GB (1) | GB1542957A (de) |
ZA (1) | ZA761470B (de) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4197137A (en) * | 1978-07-12 | 1980-04-08 | Ishikawajima-Harima Jukogyo Kabushiki Kaisha | Process and apparatus for calcining finely divided cement raw materials including finely divided combustible materials |
US4249892A (en) * | 1975-12-24 | 1981-02-10 | Klockner-Humboldt-Deutz Ag | Method and apparatus for the thermal treatment of pulverulent material particularly for the calcining of cement |
US4299564A (en) * | 1978-04-10 | 1981-11-10 | Klockner-Humboldt-Deutz Ag | Apparatus for the thermal treatment of fine-grained material with hot gases |
US4508573A (en) * | 1981-12-02 | 1985-04-02 | Texas Industries, Inc. | Co-production of cementitious products |
US4808108A (en) * | 1985-03-22 | 1989-02-28 | Krupp Polysius Ag | Method and apparatus for the heat treatment of fine-grained material |
US6447598B2 (en) * | 1999-12-23 | 2002-09-10 | Khd Humboldt Wedag Ag | Process for the thermal treatment of meal-form raw materials |
US20060068346A1 (en) * | 2004-09-30 | 2006-03-30 | Nowakowski John J | Heating method and apparatus |
EP1923367A1 (de) | 2006-11-13 | 2008-05-21 | Lafarge | Verfahren zur Herstellung von Zement |
US20100248175A1 (en) * | 2009-03-24 | 2010-09-30 | Cain Bruce E | NOx Suppression Techniques for a Rotary Kiln |
US20100244337A1 (en) * | 2009-03-24 | 2010-09-30 | Cain Bruce E | NOx Suppression Techniques for an Indurating Furnace |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5482055U (de) * | 1977-11-24 | 1979-06-11 | ||
DE2801161B2 (de) * | 1978-01-12 | 1981-06-25 | Babcock Krauss-Maffei Industrieanlagen GmbH, 8000 München | Verfahren und Brennen von Sintergut aus karbonatischen Rohstoffen wie z.B. Zementklinker |
JPS5777056A (en) * | 1980-10-30 | 1982-05-14 | Nihon Cement | Cement raw material calcining method |
DE3417148A1 (de) * | 1984-05-09 | 1985-11-14 | Krupp Polysius Ag, 4720 Beckum | Anlage zur waermebehandlung von feinkoernigem gut |
DE3520058A1 (de) * | 1985-06-04 | 1986-12-04 | O & K Orenstein & Koppel Ag, 1000 Berlin | Verfahren zur waermebehandlung von feinkoernigem gut |
DE10155407B4 (de) | 2001-11-10 | 2010-02-18 | Khd Humboldt Wedag Gmbh | Verfahren und Einrichtung zur Einführung von festem, flugfähigem Brennstoff in den Calcinator einer Zementproduktionslinie |
DE102006023980A1 (de) * | 2006-05-22 | 2007-11-29 | Polysius Ag | Anlage zur Herstellung von Zementklinker |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3203681A (en) * | 1962-12-15 | 1965-08-31 | Rosa Josef | Method for heat treatment of powdered raw meterial |
US3212764A (en) * | 1959-10-17 | 1965-10-19 | Kloeckner Humboldt Deutz Ag | Method and apparatus for heating and burning cement raw material, containing alkali |
US3955995A (en) * | 1972-12-11 | 1976-05-11 | F. L. Smidth & Co. | Calcination of pulverous material |
US3957521A (en) * | 1973-02-13 | 1976-05-18 | Polysius Ag | Method and apparatus for the heat treatment of fine-grained material |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2324565C3 (de) * | 1973-05-15 | 1982-09-02 | Krupp Polysius Ag, 4720 Beckum | Vorrichtung zur Wärmebehandlung von feinkörnigem Gut |
-
1975
- 1975-03-10 DE DE2510312A patent/DE2510312C3/de not_active Expired
-
1976
- 1976-03-03 AU AU11642/76A patent/AU507678B2/en not_active Expired
- 1976-03-04 ES ES445778A patent/ES445778A1/es not_active Expired
- 1976-03-09 BR BR7601421A patent/BR7601421A/pt unknown
- 1976-03-09 US US05/665,327 patent/US4066470A/en not_active Expired - Lifetime
- 1976-03-09 ZA ZA761470A patent/ZA761470B/xx unknown
- 1976-03-09 FR FR7606645A patent/FR2303772A1/fr active Granted
- 1976-03-09 DK DK100276A patent/DK100276A/da not_active Application Discontinuation
- 1976-03-10 GB GB9637/76A patent/GB1542957A/en not_active Expired
- 1976-03-10 CS CS761572A patent/CS219873B2/cs unknown
- 1976-03-10 JP JP51025188A patent/JPS51112833A/ja active Granted
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3212764A (en) * | 1959-10-17 | 1965-10-19 | Kloeckner Humboldt Deutz Ag | Method and apparatus for heating and burning cement raw material, containing alkali |
US3203681A (en) * | 1962-12-15 | 1965-08-31 | Rosa Josef | Method for heat treatment of powdered raw meterial |
US3955995A (en) * | 1972-12-11 | 1976-05-11 | F. L. Smidth & Co. | Calcination of pulverous material |
US3957521A (en) * | 1973-02-13 | 1976-05-18 | Polysius Ag | Method and apparatus for the heat treatment of fine-grained material |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4249892A (en) * | 1975-12-24 | 1981-02-10 | Klockner-Humboldt-Deutz Ag | Method and apparatus for the thermal treatment of pulverulent material particularly for the calcining of cement |
US4299564A (en) * | 1978-04-10 | 1981-11-10 | Klockner-Humboldt-Deutz Ag | Apparatus for the thermal treatment of fine-grained material with hot gases |
US4323397A (en) * | 1978-04-10 | 1982-04-06 | Klockner-Humboldt-Deutz Ag | Method and apparatus for the thermal treatment of fine-grained material with hot gases |
US4197137A (en) * | 1978-07-12 | 1980-04-08 | Ishikawajima-Harima Jukogyo Kabushiki Kaisha | Process and apparatus for calcining finely divided cement raw materials including finely divided combustible materials |
US4508573A (en) * | 1981-12-02 | 1985-04-02 | Texas Industries, Inc. | Co-production of cementitious products |
US4808108A (en) * | 1985-03-22 | 1989-02-28 | Krupp Polysius Ag | Method and apparatus for the heat treatment of fine-grained material |
US6447598B2 (en) * | 1999-12-23 | 2002-09-10 | Khd Humboldt Wedag Ag | Process for the thermal treatment of meal-form raw materials |
US20060068346A1 (en) * | 2004-09-30 | 2006-03-30 | Nowakowski John J | Heating method and apparatus |
US7637739B2 (en) | 2004-09-30 | 2009-12-29 | Fives North American Combustion, Inc. | Heating method and apparatus |
WO2008059378A3 (en) * | 2006-11-13 | 2008-10-30 | Lafarge Sa | Process for the production of cement |
WO2008059378A2 (en) * | 2006-11-13 | 2008-05-22 | Lafarge Sa | Process for the production of cement |
EP1923367A1 (de) | 2006-11-13 | 2008-05-21 | Lafarge | Verfahren zur Herstellung von Zement |
US20100037804A1 (en) * | 2006-11-13 | 2010-02-18 | Lafarge | Process for the production of cement |
US8252109B2 (en) | 2006-11-13 | 2012-08-28 | Lafarge | Process for the production of cement |
AU2007320876B2 (en) * | 2006-11-13 | 2012-12-13 | Lafarge Sa | Process for the production of cement |
CN101558021B (zh) * | 2006-11-13 | 2013-06-19 | 拉法基公司 | 水泥的制备方法 |
KR101625312B1 (ko) | 2006-11-13 | 2016-05-27 | 라파르쥐 | 시멘트의 제조 방법 |
US20100248175A1 (en) * | 2009-03-24 | 2010-09-30 | Cain Bruce E | NOx Suppression Techniques for a Rotary Kiln |
US20100244337A1 (en) * | 2009-03-24 | 2010-09-30 | Cain Bruce E | NOx Suppression Techniques for an Indurating Furnace |
US8662887B2 (en) | 2009-03-24 | 2014-03-04 | Fives North American Combustion, Inc. | NOx suppression techniques for a rotary kiln |
Also Published As
Publication number | Publication date |
---|---|
BR7601421A (pt) | 1976-09-14 |
AU1164276A (en) | 1977-09-08 |
DE2510312B2 (de) | 1977-12-29 |
ZA761470B (en) | 1977-03-30 |
DE2510312C3 (de) | 1982-08-26 |
CS219873B2 (cs) | 1983-03-25 |
DE2510312A1 (de) | 1976-09-16 |
FR2303772A1 (fr) | 1976-10-08 |
JPS51112833A (en) | 1976-10-05 |
JPS6144826B2 (de) | 1986-10-04 |
FR2303772B1 (de) | 1982-04-30 |
DK100276A (da) | 1976-09-11 |
GB1542957A (en) | 1979-03-28 |
AU507678B2 (en) | 1980-02-21 |
ES445778A1 (es) | 1977-11-01 |
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